JP5930758B2 - Photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition which is cured by irradiation with actinic rays and useful as a flat panel display, a coating agent, an ink, a paint, an adhesive, a resist pattern or a ceramic electronic component.

  Currently, flat panel displays (FPDs) represented by liquid crystal displays (LCDs) and plasma displays (PDPs) are indispensable for many electronic devices such as personal computers, televisions, and mobile phones, and constitute FPDs. The demand for many optical materials is also growing significantly. In recent years, the panel size has been increasing, and the development of various photosensitive resins has also become important. In particular, it has high heat resistance, high adhesion, high transparency, releasability and antistatic properties. There is a demand for a photosensitive resin having both.

  In general, when coating on a plastic substrate, high heat resistance and high adhesion are contradictory items (decreasing melt viscosity to improve substrate adhesion results in poor heat resistance) In order to solve this problem, a photosensitive composition containing colloidal silica (for example, Patent Document 1) has been proposed.

  However, in the inorganic filler addition system, if the silane concentration in the coating layer is low, sufficient heat resistance is not expressed, and if the silane concentration is high, the adhesion of the coating film is poor, cracking occurs when released from the mold, There were also problems such as high costs.

JP 2009-185548 A

  An object of the present invention is to provide a photosensitive composition that provides a cured film that exhibits high adhesion, high transparency, excellent releasability and antistatic properties without impairing the high heat resistance of the coating film. is there.

  The inventors of the present invention have reached the present invention as a result of studies to achieve the above object. That is, the present invention includes pentaerythritol (tri and / or tetra) (meth) acrylate (A), tri (meth) acrylate (B) of an alkylene oxide adduct of trimethylolpropane having a number average molecular weight of 350 to 100,000. A photosensitive composition comprising dipentaerythritol (penta and / or hexa) (meth) acrylate (C), trimethylolpropane tri (meth) acrylate (D) and a polymerization initiator (E); and A cured product obtained by curing the above composition with actinic rays.

The photosensitive composition of the present invention has the following effects.
(1) A cured product obtained by curing the composition of the present invention exhibits high heat resistance.
(2) The hardened | cured material formed by hardening | curing the composition of this invention expresses the high adhesiveness to a coating film.
(3) A cured product obtained by curing the composition of the present invention exhibits high transparency.
(4) A cured product obtained by curing the composition of the present invention exhibits high releasability.
(5) A cured product obtained by curing the composition of the present invention exhibits high antistatic properties.

The photosensitive composition curable with actinic rays of the present invention comprises pentaerythritol (tri and / or tetra) (meth) acrylate (A), an alkylene oxide adduct of trimethylolpropane having a number average molecular weight of 350 to 100,000. It contains tri (meth) acrylate (B), dipentaerythritol (penta and / or hexa) (meth) acrylate (C), trimethylolpropane tri (meth) acrylate (D) and polymerization initiator (E). (A), (B), (C) and (D) may each be used alone or in combination of two or more.
Unless (A), (B), (C) and (D) are all contained in the photosensitive composition, it is difficult to improve both the heat resistance and the adhesion of the cured product.
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.
The actinic ray in the present invention is a ray having a wavelength of 10 to 830 nm.

The pentaerythritol (tri and / or tetra) (meth) acrylate (A) in the present invention is any one of the following (Ai) to (A-iii).
(Ai) Pentaerythritol tri (meth) acrylate (A-ii) Pentaerythritol tetra (meth) acrylate (A-iii) A mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate

  The content of pentaerythritol (tri and / or tetra) (meth) acrylate (A) in the photosensitive composition of the present invention is based on the weight of the photosensitive composition from the viewpoint of heat resistance and adhesion of the cured product. Is preferably 1 to 90% by weight, more preferably 2 to 80% by weight.

  The number average molecular weight (molecular weight in the case of a single product) of tri (meth) acrylate (B) of the trimethylolpropane alkylene oxide adduct used in the present invention is 350 to 10 from the viewpoint of heat resistance and adhesion of the cured product. It is 10,000, preferably 380 to 50,000, more preferably 400 to 10,000. The number average molecular weight of the tri (meth) acrylate (B) of the alkylene oxide adduct of trimethylolpropane is particularly preferably 2000 or less, more preferably 1500 or less, and most preferably 1250 or less.

The number average molecular weight in the present invention is measured under the following conditions.
Apparatus: High-temperature gel permeation chromatography Solvent: Tetrahydrofuran Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 40 ° C

The alkylene oxide of trimethylolpropane alkylene oxide adduct tri (meth) acrylate (B) includes ethylene oxide, propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide. , Α-olefin oxide (having 5 to 30 or more carbon atoms), styrene oxide, and a combination of two or more of these (when used in combination, any of random addition, block addition, or a combination thereof) may be used. Is mentioned.
Specific examples of (B) include compounds represented by the following general formula (1).

In the formula, R ¹ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently an ethylene group, 1,2-propylene group and 1,4-butylene. It is at least one group selected from the group, m, n and p are each independently an integer of 0 to 25, and the total of m, n and p is 1 or more.

Among these, as the tri (meth) acrylate (B) of the alkylene oxide adduct of trimethylolpropane, R ² , R ³ and R ⁴ are preferably ethylene groups from the viewpoint of heat resistance and adhesion of the cured product. [Tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane], more preferably tri (meth) acrylate of ethylene oxide 3 mol adduct of trimethylolpropane, more preferably ethylene of trimethylolpropane. This is a triacrylate of an oxide 3 mol adduct.

  The content of tri (meth) acrylate (B) in the alkylene oxide adduct of trimethylolpropane having a number average molecular weight of 350 to 100,000 in the photosensitive composition of the present invention is from the viewpoint of heat resistance and adhesion. It is preferably 1 to 90% by weight, more preferably 2 to 80% by weight, based on the weight of the photosensitive composition.

The dipentaerythritol (penta and / or hexa) (meth) acrylate (C) in the present invention is any of the following (Bi) to (B-iii).
(Bi) dipentaerythritol penta (meth) acrylate (B-ii) dipentaerythritol hexa (meth) acrylate (B-iii) dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate blend

  The content of dipentaerythritol (penta and / or hexa) (meth) acrylate (C) in the photosensitive composition of the present invention is based on the weight of the photosensitive composition from the viewpoint of heat resistance and adhesion. Preferably it is 1 to 90 weight%, More preferably, it is 2 to 80 weight%.

  The content of trimethylolpropane tri (meth) acrylate (D) in the photosensitive composition of the present invention is preferably 1 to 90 weights based on the weight of the photosensitive composition from the viewpoint of heat resistance and adhesion. %, More preferably 2 to 80% by weight.

  Examples of the polymerization initiator (E) used in the photosensitive composition of the present invention include acylphosphine oxide derivative polymerization initiator (E1), α-aminoacetophenone derivative polymerization initiator (E2), and benzyl ketal derivative polymerization initiation. Agent (E3), α-hydroxyacetophenone derivative polymerization initiator (E4), benzoin derivative polymerization initiator (E5), oxime ester derivative polymerization initiator (E6), titanocene derivative polymerization initiator (E7), organic A peroxide type polymerization initiator (E8), an azo compound type polymerization initiator (E9), and other radical initiators (E10) may be mentioned. (E) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the acylphosphine oxide derivative polymerization initiator (E1) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF (Lucirin TPO)] and bis (2,4,6-trimethylbenzoyl)- And phenylphosphine oxide [manufactured by BASF (Irgacure 819)].

  Examples of the α-aminoacetophenone derivative polymerization initiator (E2) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF (Irgacure 907)], 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF (Irgacure 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF (Irgacure 379)].

  Examples of the benzyl ketal derivative polymerization initiator (E3) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF (Irgacure 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (E4), for example, 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF (Irgacure 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [BASF (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [BASF (Irgacure 2959) ] And 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF (Irgacure 127)] Can be mentioned.

  Examples of the benzoin derivative-based polymerization initiator (E5) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Examples of the oxime ester derivative polymerization initiator (E6) include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF (Irgacure OXE 01)] and Examples include ethanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (O-acetyloxime) [manufactured by BASF (Irgacure OXE 02)].

  As titanocene derivative polymerization initiator (E7), for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl ) Titanium [manufactured by BASF (Irgacure 784)].

  Examples of the organic peroxide polymerization initiator (E8) include benzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, n- Butyl 4,4-di- (t-butylperoxy) valerate, di- (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5, -dimethyl- 2,5, -di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3 , -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl high B peroxide and t- butyl trimethylsilyl peroxide.

  Examples of the azo compound polymerization initiator (E9) include 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2, 2'-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of other radical polymerization initiator (E10) include 2,3-dimethyl-2,3-diphenylbutane.

  Among these, acylphosphine oxide derivative polymerization initiators (E1), α-aminoacetophenone derivative polymerization initiators (E2), benzyl ketal derivative polymerization initiators (E3), are preferable from the viewpoint of photocurability. The α-hydroxyacetophenone derivative polymerization initiator (E4), the benzoin derivative polymerization initiator (E5), the oxime ester derivative polymerization initiator (E6) and the titanocene derivative polymerization initiator (E7) are more preferable. It is an acylphosphine oxide derivative polymerization initiator (E1).

  The content of the polymerization initiator (E) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight, more preferably, based on the weight of the photosensitive composition, from the viewpoint of photocurability. 0.1 to 20% by weight.

  The photosensitive composition of the present invention can further contain an amidine salt compound (F) if necessary. By containing (F), antistatic properties are improved. The amidine salt compound (F) in the present invention is composed of a quaternized cation and an anion, and this cation is a quaternized product of a cyclic amidine compound (F1) having 3 to 50 carbon atoms. On the other hand, the anion is an anion of an acidic compound (F2) having 5 to 50 carbon atoms containing both an aromatic ring and at least one selected from the group consisting of a carboxyl group, a sulfonyl group and a phosphonyl group. Further, the amidine salt compound (F) in the present invention does not contain a radical reactive group selected from the group consisting of a (meth) acryl group, a vinyl group, a propenyl group, an allyl group, a maleoyl group, and a fumaroyl group.

  Examples of the cyclic amidine compound (F1) include a compound having an imidazole ring (F11), a compound having a 2-imidazoline ring (F12), a compound having a tetrahydropyrimidine ring (F13), and a 1,8-diazabicyclo [5.4. 0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene. (F1) may be used alone or in combination of two or more.

  Examples of the compound (F11) having an imidazole ring include an imidazole homologue (F111), an oxyalkyl derivative (F112), a nitro and amino derivative (F113), and a benzimidazole compound (F114).

  Examples of the imidazole homologue (F111) include 1-methylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl-2-benzylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole and Examples include 1,4-dimethyl-2-ethylimidazole and 1-ethyl-3-methylimidazole.

  Examples of the oxyalkyl derivative (F112) include 1-methyl-2-oxymethylimidazole, 1-methyl-2-oxyethylimidazole, 1-methyl-4-oxymethylimidazole, 1- (β-oxyethyl) -imidazole, Examples include 1-methyl-2-ethoxymethylimidazole and 1-ethoxymethyl-2-methylimidazole.

  Examples of the nitro and amino derivatives (F113) include 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-4 (5) -nitroimidazole, and 1,2-dimethyl-5 (4) -aminoimidazole. 1-methyl-4 (5)-(2-aminoethyl) imidazole and 1- (β-aminoethyl) imidazole.

  Examples of the benzimidazole compound (F114) include 1-methylbenzimidazole, 1-methyl-2-benzylbenzimidazole, and 1-methyl-5 (6) -nitrobenzimidazole.

  Examples of the compound (F12) having a 2-imidazoline ring include 1-methylimidazoline, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl- 2-phenylimidazoline, 1-methyl-2-benzylimidazoline, 1-methyl-2-oxyethylimidazoline, 1-methyl-2-heptylimidazoline, 1-methyl-2-undecylimidazoline, 1-methyl-2-hepta Examples include decylimidazoline, 1- (β-oxyethyl) -2-methylimidazoline, 1-methyl-2-ethoxymethylimidazoline, and 1-ethoxymethyl-2-methylimidazoline.

  Specific examples of the compound (F13) having a tetrahydropyrimidine ring include 1-methyl-1,4,5,6-tetrahydropyrimidine and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine.

  Among these, from the viewpoint of antistatic properties, 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1-methylbenzimidazole, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5.4.0]- 7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene.

  Examples of the acidic compound (F2) having 5 to 50 carbon atoms containing at least one selected from the group consisting of a carboxyl group, a sulfonyl group and a phosphonyl group and an aromatic ring in the molecule include an acidic compound containing a carboxyl group (F2). F21), an acidic compound (F22) containing a sulfonyl group, and an acidic compound (F23) containing a phosphonyl group. (F2) may be used alone or in combination of two or more.

Examples of the acidic compound (F21) containing a carboxyl group include benzoic acid and alkyl-substituted benzoic acid.
Examples of the acidic compound (F22) containing a sulfonyl group include benzenesulfonic acid and alkyl-substituted benzenesulfonic acid.
Examples of the acidic compound (F23) containing a phosphonyl group include benzenephosphonic acid and alkyl-substituted benzenephosphonic acid.

  Of these, alkyl-substituted benzenesulfonic acid is preferable from the viewpoint of antistatic properties.

  As a method of synthesizing the amidine salt compound (F) from the cyclic amidine compound (F1) and the acidic compound (F2), the cyclic amidine compound (F1) is mixed by mixing the cyclic amidine compound (F1) and the acidic compound (F2). And a method of obtaining an amidine salt compound (F) composed of a quaternized cation and an anion of the acidic compound (F2).

  The content of the amidine salt compound (F) is preferably 0 to 30% by weight, more preferably 0.1 to 10% by weight, based on the weight of the photosensitive composition, from the viewpoint of antistatic properties and transparency. is there.

  The photosensitive composition of the present invention can further contain an amine salt compound (G) as necessary. By containing (G), the antistatic property is improved, and when used in combination with (F), the heat resistance, transparency and antistatic property of the cured product are further improved. The amine salt compound (G) in the present invention is composed of a quaternized cation and an anion, and this cation has a quaternized amino group of (meth) acrylate (G1) having 3 to 50 carbon atoms having an amino group. Is. On the other hand, the anion is an anion of an acidic compound (G2) having 5 to 50 carbon atoms containing both an aromatic ring and at least one selected from the group consisting of a carboxyl group, a sulfonyl group, and a phosphonyl group.

  Examples of the (meth) acrylate (G1) having 3 to 50 carbon atoms having an amino group include N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate and N, N-diethylaminoethyl acrylate. (G1) may be used alone or in combination of two or more.

  Among these, N, N-dimethyl-2-aminoethyl acrylate and N, N-diethyl-2-aminoethyl acrylate are preferable from the viewpoint of antistatic properties.

  The acidic compound (G2) having 5 to 50 carbon atoms containing at least one selected from the group consisting of a carboxyl group, a sulfonyl group and a phosphonyl group and an aromatic ring in the molecule is the same as the compound exemplified in (F2). And the preferable one is the same as (F2). (G2) may be used alone or in combination of two or more.

  The content of the amine salt compound (G) is preferably 0 to 30% by weight, more preferably 0.1 to 10% by weight, based on the weight of the photosensitive composition, from the viewpoint of antistatic properties and transparency. is there.

The photosensitive composition of this invention can contain the acid generator (H) which generate | occur | produces an acid with an actinic ray further as needed. By containing (H), curability is improved.
Examples of the acid generator (H) that generates an acid by actinic rays include a sulfonium salt derivative (H1) and an iodonium salt derivative (H2). (H) may be used alone or in combination of two or more.

  Examples of the sulfonium salt derivative (H1) include triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, [p- (phenyl mercapto ) Phenyl] diphenylsulfonium hexafluorophosphate [manufactured by San Apro Co., Ltd. [CPI-100P] and [p- (phenylmercapto) phenyl] diphenylsulfonium [tri (perfluoroethyl)] trifluorophosphate.

  Examples of the iodonium salt derivative (H2) include iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate [manufactured by Ciba Japan (DAROCUR 250)], iodonium [bis (4-t -Butylphenyl)] hexafluorophosphate, iodonium [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] trifluoro [tris ( Perfluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] [tetrakis (perfulphenyl)] borate, and a compound represented by the following chemical formula (2).

  Among these, the compound represented by the chemical formula (2) is preferable from the viewpoint of photocurability.

  The content of the acid generator (H) is preferably 0 to 30% by weight, more preferably 0.01 to 20% by weight, based on the weight of the photosensitive composition, from the viewpoint of photocurability. The acid generator (H) is preferably used in combination with the amidine salt compound (F). The acid generator (H) is preferably used in combination with the amine salt compound (G). The acid generator (H) is preferably used in combination with the amidine salt compound (F) and the amine salt compound (G).

The photosensitive composition of the present invention can further contain a mold releasability imparting agent (I) as necessary. By containing (I), the releasability from the mold is improved.
The mold releasability-imparting agent (I) in the present invention is composed of a quaternized cation and an anion, and the cation is a tertiary amine having 3 to 150 carbon atoms (I21) and / or a cyclic having 3 to 50 carbon atoms. This is a quaternized version of the amidine compound (I22). On the other hand, the anion is an anion of a phosphate ester (I1) having 1 to 150 carbon atoms.
(I) may be used individually by 1 type, and may use 2 or more types together.

  The mold releasability imparting agent (I) has a molar ratio (I1) / [(I21) and / or (I22)] of preferably 0.75 to 2.00, more preferably 1.00. ~ 1.75. When the molar ratio (I1) / [(I21) and / or (I22)] is 0.75 or more, the resin is not incompatible and the transparency of the cured product is not impaired. Moreover, there is no possibility that hardened | cured material may decompose | disassemble with an acid at the time of high temperature environment as it is 1.75 or less.

  As the phosphate ester (I1) having 1 to 150 carbon atoms, a phosphate ester of primary or secondary alkyl (1 to 30 carbon atoms such as 2-ethylhexyl, dodecyl and octadecyl), or primary or secondary Examples thereof include phosphate esters of adducts of 1 to 30 moles of alkylene oxide (2 to 4 carbon atoms) of alcohol (C1 to C20, such as isopropanol and octanol). Among these, from the viewpoint of releasability, a primary or secondary alkyl (carbon number 1 to 30) phosphate ester is preferable. (I1) may be used alone or in combination of two or more.

  The phosphate ester (I1) is composed of a monoester and a diester, and the molar ratio is preferably 0.8 / 1 to 1.2 / 1, more preferably 0.9 / 1 to 1.1 /. 1. When the molar ratio is 0.8 / 1 or more, bleeding out from the resin is easy, and the releasability from the mold is good. When the ratio is 1.2 / 1 or less, the amount of bleed out from the resin does not increase excessively, and the adhesion to the base resin is good.

  The tertiary amine having 3 to 150 carbon atoms (I21) includes tertiary aliphatic amines having 3 to 50 carbon atoms (for example, hexadecyldimethylamine and octadecyldimethylamine), primary or secondary aliphatic amines (carbon Examples include tertiary amines such as alkylene oxides (2 to 4 carbon atoms) of 1 to 30 moles adducts of a number of 3 to 30, for example, octadecylamine and diethylamine. Among these, from the viewpoint of releasability, a tertiary aliphatic amine having 4 to 30 carbon atoms is preferable, and a tertiary aliphatic amine having 15 to 20 carbon atoms is more preferable. (I21) may be used alone or in combination of two or more.

  Examples of the cyclic amidine compound (I22) having 3 to 50 carbon atoms include the same as those exemplified as the cyclic amidine compound (F1), and preferred ones are also the same. (I22) may be used alone or in combination of two or more.

  The content of the mold releasability imparting agent (I) is preferably 0 to 5 weights based on the weight of the photosensitive composition from the viewpoint of releasability from the mold and adhesion to the base resin. %, More preferably 0.05 to 3% by weight. The mold releasability imparting agent (I) is preferably used in combination with the acid generator (H).

  The photosensitive composition of the present invention can further contain a radically polymerizable compound (J) other than (A) to (D) and (G), if necessary. ) Acrylamide compound (J1), (meth) acrylate compound (J2) other than (A) to (D) and (G) having 4 to 35 carbon atoms, aromatic vinyl compound (J3) having 6 to 35 carbon atoms, carbon The vinyl ether compound (J4) of several 3 to 35 and other radically polymerizable compounds (J5) are mentioned. (J) may be used alone or in combination of two or more.

  Examples of the (meth) acrylamide compound (J1) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- n-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide and N, N-diethyl (meth) acrylamide.

Examples of the (meth) acrylate compound (J2) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.
The “monofunctional to hexafunctional (meth) acrylate” means a (meth) acrylate having 1 to 6 (meth) acryloyl groups, and the same description method is used hereinafter.
Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, and decyl (meth) acrylate. , Isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, Benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl ( Acrylate), cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexylcarbyl Tall (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (Meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) a Relate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyl Roxypropyl (meth) acrylate, diethylene glycol monovinyl ether monoacrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) ) Acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, Polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide Monoalkyl ether (meth) acrylate, oligopropylene Oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, tri Fluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide modified phenol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, ethylene oxide modified Nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate and ethylene oxide modified-2-ethylhex Le (meth) acrylate.

  Examples of the bifunctional (meth) acrylate include 1,4-butanedi (meth) acrylate, 1,6-hexanediacrylate, polypropylene diacrylate, 1,6-hexanediol di (meth) acrylate, and 1,10-decane. Diol di (meth) acrylate, neopentyl diacrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxy Cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, ethyl Oxide modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A Examples include di (meth) acrylate and tricyclodecane di (meth) acrylate.

  Examples of trifunctional (meth) acrylates include trimethylolethane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, and dipentapropionic acid. Examples include erythritol tri (meth) acrylate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

  Examples of tetrafunctional (meth) acrylates include sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and ethoxylated pentaerythritol tetra (meth) acrylate. It is done.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate.

  Examples of the hexafunctional (meth) acrylate include sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (J3) include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, and acetoxy styrene. , Chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butyl Styrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene Emissions, isopropenyl styrene, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, and 4-methoxystyrene and 4-t-butoxystyrene.

Examples of the vinyl ether compound (J4) having 3 to 35 carbon atoms include the following monofunctional or polyfunctional vinyl ethers.
In addition, said monofunctional or polyfunctional vinyl ether means a vinyl ether in which the number of vinyl ether groups is one or more, respectively.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

  Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  Other radical polymerizable compounds (J5) include, for example, acrylonitrile, vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), allyl ester compounds (such as allyl acetate), and halogen-containing monomers (vinylidene chloride). And vinyl chloride) and olefin compounds (ethylene, propylene, etc.).

  Among these, from the viewpoint of curing speed, the acrylamide compound (J1) having 3 to 35 carbon atoms, the (meth) acrylate compound (J2) having 4 to 35 carbon atoms, and the aromatic vinyl compound having 6 to 35 carbon atoms are preferable. (J3) and a vinyl ether compound (J4) having 3 to 35 carbon atoms, more preferably an acrylamide compound (J1) having 3 to 35 carbon atoms and a (meth) acrylate compound (J2) having 4 to 35 carbon atoms. .

The content of the radical polymerizable compound (J) is preferably in the range of 0 to 60% by weight, more preferably 0 to 10% by weight in the photosensitive composition.
In (J), the content of the monofunctional (meth) acrylate having a hydroxyl group and a polyoxyalkylene chain is preferably 5% by weight or less. When content is 5 weight% or less, the heat resistance and adhesiveness of hardened | cured material further improve.

  The photosensitive composition of this invention can contain a coloring agent, a metal oxide powder, and / or a metal powder as needed. These may be used individually by 1 type and may use 2 or more types together.

  Examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

  Examples of organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide, pyrazolone, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid, and the like. Insoluble azo pigments such as acid anilide, acetoacetanilide monoazo, acetoacetanilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal free phthalocyanine And polycyclic or heterocyclic compounds such as isocindolinone, quinacridone, dioxazine, perinone and perylene.

  Specific examples of dyes include yellow dyes, for example, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, or open-chain active methylene compounds as coupling components, and open-chains as coupling components. Azomethine dyes having an active methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes .

  Examples of magenta dyes include phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) as coupling components ) Aryl or heteryl azo dyes, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, arylidene dyes, styryl dyes, merocyanines such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes And quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  Examples of the cyan dye include azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, Examples of the anthraquinone dyes include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives having aryl or heteryl azo dyes (such as CI Direct Blue 14) and indigo / thioindigo dyes as coupling components.

  Examples of the metal oxide powder include titanium oxide, aluminum oxide, barium titanate, calcium zirconate, niobium oxide, and lead zirconate titanate.

  Examples of the metal powder include palladium, nickel, copper, silver, and gold.

  The particle diameter of the colorant, metal oxide powder and / or metal powder is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm as the average particle diameter from the viewpoint of the sharpness of the coating film. preferable.

  Although the total addition amount of a coloring agent, a metal oxide powder, and / or a metal powder is not specifically limited, It is preferable to add in the range of 0 to 60 weight% in the photosensitive composition.

When using the pigment, the metal oxide powder and / or the metal powder in the photosensitive composition of the present invention, it is preferable to add a pigment dispersant in order to improve the dispersibility and the storage stability of the photosensitive composition.
Examples of the pigment dispersant include a pigment dispersant manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184). Or 2020), pigment dispersants manufactured by Ajinomoto Fine Techno Co., Ltd. (Ajisper PB711, PB821, PB814, PN411, PA111, etc.), and pigment dispersants manufactured by Lubrizol Corporation (Solspers 5000, 12000, 32000, 33000, 39000, etc.). . These pigment dispersants may be used alone or in combination of two or more. Although the addition amount of a pigment dispersant is not specifically limited, It is preferable to use in the range of 0 to 20 weight% in the photosensitive composition.

  The photosensitive composition of the present invention can contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent), a leveling agent, a polymerization inhibitor, and the like as necessary.

Solvents include glycol ethers (ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether acetate and propylene). Glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran and 1,8 -Cineol etc.). These may be used alone or in combination of two or more.
The content of the solvent is preferably 0 to 95% by weight based on the weight of the photosensitive composition, more preferably 3 to 94% by weight, and particularly preferably 5 to 90% by weight.

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight based on the weight of the photosensitive composition, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The content of the adhesion-imparting agent is preferably 0 to 20% by weight based on the weight of the photosensitive composition, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight.

  Examples of the leveling agent include fluorine-based leveling agents (perfluoroalkylethylene oxide adducts and the like) and silicone-based leveling agents (amino polyether-modified silicone, methoxy-modified silicone, polyether-modified silicone, and the like). The content of the leveling agent is preferably 2% by weight or less, more preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.1% by weight from the viewpoint of the effect of addition and transparency based on the weight of the photosensitive composition. 0.5% by weight.

  Examples of the polymerization inhibitor include hydroquinone and methyl ether hydroquinone. The content of the polymerization inhibitor is preferably 0 to 1% by weight, more preferably 0 to 0.1% by weight, based on the weight of the photosensitive composition.

  The photosensitive composition of the present invention further contains inorganic fine particles, a dispersant, an antifoaming agent, a thixotropy imparting agent, a slip agent, a flame retardant, an antioxidant, an ultraviolet absorber and the like in accordance with the purpose of use. Can do.

  The photosensitive composition of the present invention comprises pentaerythritol (tri and / or tetra) (meth) acrylate (A), a tri (meth) acrylate of an alkylene oxide adduct of trimethylolpropane having a number average molecular weight of 350 to 100,000. (B), dipentaerythritol (penta and / or hexa) (meth) acrylate (C), trimethylolpropane tri (meth) acrylate (D) and polymerization initiator (E), and optionally containing a radical reactive group Amidine salt compound (F), amine salt compound (G) containing radical reactive group, acid generator (H), mold release agent (I), other radical polymerizable compound (J), And a solvent and other components are mixed and stirred with a disperser or the like. The mixing and stirring temperature is usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C.

Examples of the method for applying the photosensitive composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and planographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing. A known printing method can be applied. In addition, ink-jet coating that continuously discharges fine droplets can also be applied.
A coating film thickness is 0.5-300 micrometers normally as a film thickness after hardening drying. The upper limit is preferably 250 μm from the viewpoints of drying properties and curability, and the lower limit is preferably 1 μm from the viewpoints of wear resistance, solvent resistance, and contamination resistance.

  When using the photosensitive composition of this invention diluted with a solvent, it is preferable to dry after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.

  As an energy source for curing the photosensitive composition of the present invention by irradiation with actinic rays, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, etc. (UV / EB curing) The latest trends in technology, edited by Radtech Institute, CM Publishing, 138 pages, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Heating may be performed for the purpose of diffusing the base generated from the photobase generator during and / or after irradiation with actinic rays. The heating temperature is usually 30 ° C to 200 ° C, preferably 35 ° C to 150 ° C, more preferably 40 ° C to 120 ° C.

As an energy source for curing the photosensitive composition of the present invention by electron beam irradiation, a commonly used electron beam irradiation apparatus can be used.
The irradiation amount (Mrad) of the electron beam is preferably 0.5 to 20, and preferably 1 to 15 from the viewpoint of the curability of the photosensitive composition and the flexibility of the cured product, and avoiding damage to the cured film and the substrate. It is.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

Production Example 1
[Synthesis of Amidine Salt Compound (F-1) Containing No Radical Reactive Group]
A flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump was charged with 326.50 parts of dodecylbenzenesulfonic acid as an acidic compound (F2), heated to 40 ° C., and then 1,8- Diazabicyclo [5.4.0] -7-undecene [DBU: manufactured by San Apro Co., Ltd.] 152.24 parts was added and stirred for 1 hour to obtain an amidine salt compound (F-1).

Production Example 2
[Production of Amidine Salt Compound (F-2) Containing No Radical Reactive Group]
A flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump is charged with 100 parts of benzoic acid as an acidic compound (F2), and a methanol solution of 1-ethyl-3-methylimidazolium monomethyl carbonate as a cyclic amidine compound (F1). (The solid content concentration was 70%, and the synthesis method was in accordance with the method described in JP-A-2001-316372.) 266.01 parts were added dropwise over 3 hours and aged at 50 ° C. for 1 hour. Thereafter, methanol was removed under reduced pressure to obtain an amidine salt compound (F-2).

Production Example 3
[Production of amine salt compound (G-1) containing a radical reactive group]
In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump, N, N-dimethyl-2-aminoethyl acrylate (“DMAEA” manufactured by Kojin Co., Ltd.) 143 as (meth) acrylate (G1) having an amino group was added. .18 parts, 326.50 parts of dodecylbenzenephosphonic acid was added as acidic compound (G2), and the mixture was stirred at 25 ° C. for 1 hour to obtain amine salt compound (G-1).

Production Example 4
[Production of Amine Salt Compound (G-2) Containing Radical Reactive Group]
In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump, N, N-dimethyl-2-aminopropyl acrylate having an amino group (G1) (“DMPAA” manufactured by Kojin Co., Ltd.) 156 .22 parts and 326.50 parts of dodecylbenzenesulfonic acid as an acidic compound (G2) were added and stirred at 25 ° C. for 1 hour to obtain an amine salt compound (G-2).

Production Example 5
[Production of Acid Generator (H-1) {Compound Represented by Chemical Formula (2)}]

  In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump, 6.5 parts of toluene, 8.1 parts of isopropylbenzene, 5.35 parts of potassium iodide, and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid. Then, a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour while maintaining the temperature at 10 ± 2 ° C. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed three times with water, and the organic solvent was distilled off under reduced pressure to obtain 5.0 parts of the desired acid generator (H-1) (pale yellow solid). It was.

Production Example 6
[Production of mold releasability imparting agent (I-1)]
In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump, 2-ethylhexyl phosphate ester (“AP-8” manufactured by Daihachi Chemical Industry Co., Ltd.) as a phosphate ester (I1) 68.46 parts, grade 3 66.38 parts of octadecyldimethylamine was added as amine (I21), and the mixture was stirred at 25 ° C. for 1 hour to obtain a mold releasability-imparting agent (I-1).

Production Example 7
[Production of mold releasability-imparting agent (I-2)]
In a flask equipped with a stirrer, a condenser, a thermometer, and a dropping pump, 48.7 parts of dodecyl phosphate ester (“Phoslex A-180L” manufactured by SC Organic Chemical Co., Ltd.) as the phosphate ester (I1), cyclic amidine compound (I22) ), 1,30-diazabicyclo [5.4.0] -7-undecene [DBU: manufactured by San Apro Co., Ltd.], 22.30 parts, and stirred at 25 ° C. for 1 hour to obtain a mold releasability imparting agent ( I-2) was obtained.

Example 1
Pentaerythritol tetraacrylate [Sanyo Chemical Industries, Ltd. “Neomer EA-300”] (A-1) 7.1 parts, triacrylate of ethylene oxide adduct of trimethylolpropane having a number average molecular weight of 430 [Toagosei “M-350” (B-1) 14.6 parts, dipentaerythritol penta / hexaacrylate [“Neomer DA-600” manufactured by Sanyo Chemical Industries, Ltd .; penta / hexa (weight ratio) = 50 / 50] (C-1) 13.8 parts, trimethylolpropane triacrylate [“M-309” manufactured by Toagosei Co., Ltd.] (D-1) 6.3 parts, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide [BASF “Irgacure 819”] (E-1) 1.9 parts and 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one [BASF (Irgacure 907)] (E-2) 0.63 part, Irganox 1135 [BASF property] 0.2 part as an antioxidant and Irganox L57 [ BASF property] 0.2 parts, Tinuvin 400 [manufactured by BASF] 0.25 part as an ultraviolet absorber, and 43.9 parts methyl ethyl ketone and 11.0 parts methyl isobutyl ketone as a solvent are mixed together and uniformly with a disperser The mixture was stirred and the photosensitive composition (Q-1) of this invention was obtained.

Example 2
“Pentaerythritol tetraacrylate (A-1) 7.1 parts” is replaced with “pentaerythritol tri / tetraacrylate [“ light acrylate PE-3A ”manufactured by Kyoeisha Chemical Co., Ltd .; tri / tetra (weight ratio) = 35/65]. (A-2) 50 parts ”is replaced with“ 14.6 parts of triacrylate (B-1) trimethylolpropane adduct of trimethylolpropane having a number average molecular weight of 430 ”and“ trimethylolpropane having a number average molecular weight of 1200 ”. Ethylene oxide adduct triacrylate [Shin Nakamura Chemical Co., Ltd. "NK Ester AT-20E" (B-2) 50 parts] to "dipentaerythritol penta / hexaacrylate (C-1) 13.8 parts""" Dipentaerythritol hexaacrylate [Kyoeisha Chemical Co., Ltd. "Light acrylate DPE-6A ] Was changed to (C-2) 100 parts "means to obtain a photosensitive composition of the present invention in the same manner as in Example 1 (Q-2).

Example 3
“Pentaerythritol tetraacrylate (A-1) 7.1 parts” is replaced with “pentaerythritol tri / tetraacrylate [M-305” manufactured by Toagosei Co., Ltd .; tri / tetra (weight ratio) = 40/60] (A -3) 80 parts "to" 14.6 parts of triacrylate (B-1) trimethylolpropane ethylene oxide adduct having a number average molecular weight of 430 "and" propylene oxide of trimethylolpropane having a number average molecular weight of 470 " The photosensitive composition (Q of the present invention) was used in the same manner as in Example 1 except that the adduct was changed to triacrylate [Sanyo Chemical Industries, Ltd. “Neomer TA-505” (B-3) 80 parts] ”. -3) was obtained.

Example 4
“Pentaerythritol tetraacrylate (A-1) 7.1 parts” is changed to “pentaerythritol tetramethacrylate [Sartomer Co., Ltd.] (A-4) 100 parts” and “trimethylolpropane triacrylate (D-1) 6”. .3 parts "is changed to" trimethylolpropane trimethacrylate ["Kyoeisha Chemical Co., Ltd." Light Ester TMP "" (D-2) 100 parts "] A composition (Q-4) was obtained.

Example 5
A photosensitive composition (Q-5) of the present invention was obtained in the same manner as in Example 1 except that “pentaerythritol tetraacrylate (A-1)” was changed from 7.1 parts to 300 parts.

Example 6
The photosensitivity of the present invention was the same as in Example 1, except that “triacrylate (B-1) of ethylene oxide adduct of trimethylolpropane having a number average molecular weight of 430” was changed from 14.6 parts to 300 parts. A composition (Q-6) was obtained.

Example 7
A photosensitive composition (Q-7) of the present invention was obtained in the same manner as in Example 1 except that “dipentaerythritol penta / hexaacrylate (C-1)” was changed from 13.8 parts to 300 parts. .

Example 8
A photosensitive composition (Q-8) of the present invention was obtained in the same manner as in Example 1 except that “trimethylolpropane triacrylate (D-1)” was changed from 6.3 parts to 300 parts.

Example 9
A photosensitive composition (Q-9) of the present invention was obtained in the same manner as in Example 1, except that 0.02 part of the acid generator (H-1) synthesized in Production Example 5 was newly added.

Example 10
A photosensitive composition (Q-10) of the present invention was obtained in the same manner as in Example 9, except that 0.5 part of the amidine salt compound (F-1) synthesized in Production Example 1 was newly added.

Example 11
A photosensitive composition (Q-11) of the present invention was obtained in the same manner as in Example 9, except that 0.5 part of the amidine salt compound (F-2) synthesized in Production Example 2 was newly added.

Example 12
A photosensitive composition (Q-12) of the present invention was obtained in the same manner as in Example 9, except that 0.5 part of the amine salt compound (G-1) synthesized in Production Example 3 was newly added.

Example 13
A photosensitive composition (Q-13) of the present invention was obtained in the same manner as in Example 9, except that 0.5 part of the amine salt compound (G-2) synthesized in Production Example 4 was newly added.

Example 14
A photosensitive composition (Q-14) of the present invention was obtained in the same manner as in Example 10 except that 0.5 part of the amine salt compound (G-1) synthesized in Production Example 3 was newly added.

Example 15
The photosensitive composition (Q-15) of the present invention was prepared in the same manner as in Example 9, except that 0.13 part of the mold releasability imparting agent (I-1) synthesized in Production Example 6 was newly added. Obtained.

Example 16
A photosensitive composition (Q-16) of the present invention was obtained in the same manner as in Example 9, except that 2 parts of the mold releasability imparting agent (I-2) synthesized in Production Example 7 was newly added. .

Example 17
As in Example 1, except that 0.5 part of N, N-dimethylaminoacrylate methyl chloride salt [“DMAEA-Q” manufactured by Kojin Co., Ltd.] is newly added as an amine salt compound other than (G). Thus, a photosensitive composition (Q-17) of the present invention was obtained.

Comparative Example 1
A comparative photosensitive composition (Q′-1) was obtained in the same manner as in Example 1 except that “pentaerythritol tetraacrylate (A-1)” was not used.

Comparative Example 2
Photosensitive composition for comparison (Q′-2) in the same manner as in Example 1 except that “triacrylate (B-1) of ethylene oxide adduct of trimethylolpropane having a number average molecular weight of 430” is not used. Got.

Comparative Example 3
A comparative photosensitive composition (Q′-3) was obtained in the same manner as in Example 1 except that “dipentaerythritol penta / hexaacrylate (C-1)” was not used.

Comparative Example 4
A comparative photosensitive composition (Q′-4) was obtained in the same manner as in Example 1 except that “trimethylolpropane triacrylate (D-1)” was not used.

[Performance evaluation of coating after curing]
Each photosensitive composition obtained in Examples 1 to 17 and Comparative Examples 1 to 4 was subjected to a surface treatment on a 100 μm thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.], and an applicator. The film was applied so as to have a film thickness of 20 μm, and was exposed using a belt conveyor type UV irradiation apparatus (“ECS-151U”, iGraphics Co., Ltd.). The exposure amount was 150 mJ / cm ² at 365 nm. In the coating film for evaluation of releasability, a photosensitive composition was applied to a PET film cut to a size of 25 mm in width and 100 mm in length, and then a titanium plate was laminated, and UV exposure was performed from the PET film side.
Table 1 shows the results of performance evaluation of the cured coating film by the following method.

[Performance evaluation method]
(1) Heat resistance test The above-mentioned cured coating film was placed in a 85 ° C. blown constant temperature thermostat (DKN302: manufactured by Yamato Kagaku Co., Ltd.) and temperature-controlled for 100 hours or 300 hours. The temperature-controlled resin film was visually observed and observed at 50 times using a shape measurement microscope (ultra-deep shape measurement microscope VK-8550, manufactured by Keyence Corporation), and evaluated according to the following criteria.
A: No change is observed at all before temperature adjustment. O: No change by visual observation, but color change is observed with a microscope.
Δ: Although there is no change visually, a change in shape and shape before temperature adjustment are observed with a microscope.
X: The change before temperature control is already visually recognized (2) Adhesiveness Adhesiveness was evaluated by a cross cellophane tape peeling test in accordance with JIS K-5400.
(3) Transmittance and haze (transparency)
Based on JIS-K7105, the transmittance and haze were measured using a total light transmittance measuring device [trade name “haze-garddual” manufactured by BYK Gardner Co., Ltd.]. In both cases, the unit is%.
(4) Releasability With respect to the coating film for evaluation of releasability, the adhesive force when peeled at a peeling speed of 10 m / min peeling angle of 180 ° was measured with a universal tensile testing machine. The measurement was performed in an environment of a temperature of 23 ° C. and a humidity of 50% RH. 0.6 N / 25 mm or less is a preferable value, and more preferably 0.2 N / 25 mm or less.
(5) Surface resistivity (antistatic property)
The above-mentioned cured coating film was measured for surface resistivity using a digital super insulation / microammeter (DSM-8103 / SME-8310: manufactured by Hioki Co., Ltd.) at 23 ° C. and evaluated according to the following criteria.
A: Surface specific resistance value is 1 × 10 ¹³ Ω or less ○: Surface specific resistance value is greater than 1 × 10 ¹³ Ω, 1 × 10 ¹⁴ Ω or less Δ: Surface specific resistance value is greater than 1 × 10 ¹⁴ Ω, 1 × 10 ¹⁵ Ω or less ×: The surface resistivity is larger than 1 × 10 ¹⁵ Ω

  In the photosensitive composition of the present invention, the cured film after curing is excellent in high heat resistance, high adhesion, high transparency, and high antistatic properties. For flat panel displays, coating agents, inks, It is useful for coatings, adhesives, resist pattern formation, or ceramic electronic component manufacturing.

Claims (11)

  Pentaerythritol (tri and / or tetra) (meth) acrylate (A), trimethylolpropane alkylene oxide adduct tri (meth) acrylate (B) having a number average molecular weight of 350 to 100,000, dipentaerythritol (penta And / or hexa) (meth) acrylate (C), trimethylolpropane tri (meth) acrylate (D), and a polymerization initiator (E). The composition according to claim 1, wherein the tri (meth) acrylate (B) of the alkylene oxide adduct of trimethylolpropane is a compound represented by the following general formula (1).

[Wherein R ¹ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are each independently an ethylene group, a 1,2-propylene group and a 1,4- It is at least one group selected from butylene groups, m, n and p are each independently an integer of 0 to 25, and the total of m, n and p is 1 or more. ]   The polymerization initiator (E) is an acylphosphine oxide derivative polymerization initiator (E1), an α-aminoacetophenone derivative polymerization initiator (E2), a benzyl ketal derivative polymerization initiator (E3), or an α-hydroxyacetophenone derivative. At least one radical polymerization selected from the group consisting of a systemic polymerization initiator (E4), a benzoin derivative polymerization initiator (E5), an oxime ester derivative polymerization initiator (E6) and a titanocene derivative polymerization initiator (E7). The composition according to claim 1 or 2, which is an initiator.   Further, the cyclic amidine compound (F1) having 3 to 50 carbon atoms, an acidic compound having 5 to 50 carbon atoms containing an aromatic ring and at least one selected from the group consisting of a carboxyl group, a sulfonyl group and a phosphonyl group in the molecule. The composition according to any one of claims 1 to 3, comprising an amidine salt compound (F) which comprises (F2) and does not contain a radical reactive group.   Furthermore, the C3-C50 (meth) acrylate (G1) which has an amino group, carbon number 5 which contains at least 1 selected from the group which consists of a carboxyl group, a sulfonyl group, and a phosphonyl group in a molecule | numerator, and an aromatic ring The composition in any one of Claims 1-4 containing the amine salt compound (G) comprised from -50 acidic compounds (G2).   Furthermore, the composition in any one of Claims 1-5 containing the acid generator (H) which generate | occur | produces an acid by actinic light.   The composition according to claim 6, wherein the acid generator (H) that generates an acid by actinic rays is a sulfonium salt derivative (H1) and / or an iodonium salt derivative (H2).   Further, a mold comprising a phosphate ester (I1) having 1 to 150 carbon atoms, a tertiary amine (I21) having 3 to 150 carbon atoms and / or a cyclic amidine compound (I22) having 3 to 50 carbon atoms. The composition according to any one of claims 1 to 7, comprising a releasability imparting agent (I).   The content of the pentaerythritol (tri and / or tetra) (meth) acrylate (A) is 1 to 90% by weight, and the content of the tri (meth) acrylate (B) of the alkylene oxide adduct of the trimethylolpropane is 1. ~ 90 wt%, the dipentaerythritol (penta and / or hexa) (meth) acrylate (C) content is 1 to 90 wt%, the trimethylolpropane tri (meth) acrylate (D) content is 1 ~ 90 wt%, the content of the polymerization initiator (E) is 0.05 to 30 wt%, the content of the amidine salt compound (F) is 0 to 30 wt%, and the content of the amine salt compound (G) is The content of the acid generator (H) is 0 to 30% by weight, the content of the mold releasability imparting agent (I) is 0 to 5% by weight, and the content of the acid generator (H) is 0 to 5% by weight. Any Narubutsu. It is an object for flat panel displays , The composition in any one of Claims 1-9.   Hardened | cured material formed by hardening | curing the composition in any one of Claims 1-10 with actinic light.